System and method for reading x-ray-fluorescence marking

ABSTRACT

In a method and a system for authenticating an object marked with XRF marking, a wavelength spectral profile is provided of a detected portion of an X-Ray signal arriving from an object in response to X-Ray or Gamma-Ray radiation applied to the object and the wavelength spectral profile is filtered to suppress trend and periodic components from the wavelength spectral profile to obtain a filtered profile with improved signal to noise or signal to clutter ratio. The object can be authenticated by processing the filtered profile and identifying one or more peaks therein, which satisfy a predetermined condition, whereby the wavelengths of the identified peaks are indicative of the signatures of materials included in the object.

TECHNOLOGICAL FIELD

The present invention is in the field of X-Ray-Fluorescence (XRF)marking and particularly relates to techniques for reading XRF signalsindicative of materials and compositions used for marking objects.

BACKGROUND

X-ray fluorescence (XRF) marking is a technique used to detect andpossibly quantify chemical material elements and/or compositionconstituents which can serve for marking an object. Theparameters/identity of an object can then be identified based on thedetected materials.

In the following, X-ray fluorescence (XRF) is used to refer to theemission of characteristic “secondary” (or fluorescent) X-rays from amaterial that has been excited by primary X-rays or gamma raysradiation. The term fluorescence refers to absorption of radiation of aspecific energy resulting in the re-emission of radiation of a differentenergy (typically lower). The X-ray fluorescence (XRF) phenomenon isbased on the fact that when materials are exposed to short-wavelengthX-rays or gamma rays, they may expel electrons from inner orbitals ofthe atom, which thus cause electrons in higher orbitals to “fall” intothe lower/inner orbital, and, in the process, release photons withenergy equal to the energy difference between the two orbitals involved.Different chemical elements have electronic orbitals/shells of differentcharacteristic energies, and therefore the spectral profile of an XRFresponse from an object/material is indicative of the chemical elementsand possibly of the amount of each element included in thematerial/object.

Counterfeiting and supply chain diversion of materials are phenomenathat impact many fields. Many materials of inferior quality, includingbut not limited to raw materials, electronics, polymers andpharmaceuticals are counterfeited by unscrupulous manufacturers andenter the supply chain, often by copying labeling associated with“brand” companies. To this end there are various techniques known in theart which utilize XRF marking to identify object/materials and determinetheir source/manufacturer/owner and/or various parameter, therebyenabling to discern between the original materials/goods and counterfeitmaterials/goods. Since chemical makeup of the original and counterfeitedmaterials may be similar, some techniques utilize additive XRF markers(such as compositions of materials having a specific a-priori known XRFsignature), which are specifically added to the object to enableidentification of the object and/or certain parameters thereof, such asits source.

For example U.S. Pat. No. 8,590,800 discloses a method of authenticatingand/or identifying an article containing a chemical marking agent, whichis substantially inseparably enclosed in a marker as a carrier andcontains selected chemical elements and/or compounds in the form ofmarker elements, in concentrations based on a predetermined encryptioncode, which method comprises the steps of: i) qualitatively and/orquantitatively identifying the marker elements of the chemical markingagent, and ii) comparing the values identified in step (i) with thepredetermined encryption code.

U.S. Pat. No. 8,864,038 discloses a material tracing technique forencoding information in a material. The technique includes storinginformation to be encoded in the material, generating a number based onthe information, determining an amount of at least one tracer to beincorporated into the material corresponding to the number, andincorporating the determined amount of the at least one tracer into thematerial. Decoding information encoded in the material includesmeasuring an amount of the at least one tracer, in some embodimentsafter tracer activation, determining a number corresponding to themeasured at least one tracer, and decoding the number to obtaininformation associated with the material.

U.S. Pat. No. 8,158,432 discloses a system for marking a fluid by amarker, the fluid flowing from a source to a destination, the systemincluding a sensor for determining a value of a fluid property and afluid flow controller for admitting a selected amount of the marker tothe fluid, wherein the selected amount is determined according to thefluid value and a predetermined concentration of the marker in the fluidin the destination.

GENERAL DESCRIPTION

Solid waste, in many countries, must be disposed of in facilitiesdesigned for disposal of such waste, such as landfills. Solid waste maycomprise construction waste, which is waste that results fromdestruction or renovation of roads, buildings and other man-madestructures. Construction waste may comprise concrete, asphalt, metal,wood, insulation materials, drywall, glass, plastic and other associateddebris.

In many countries, disposal of solid waste is associated with high costsstemming from transportation costs, to ship the waste to an appropriatedisposal facility, and disposal costs, collected by the disposalfacility to process the waste. Although contractors responsible forprivate and municipal construction are frequently required to dispose ofconstruction waste and bear the costs of such disposal, unscrupulouscontractors occasionally dispose of waste in illegal dumping grounds inorder to avoid disposal costs. Illegal dumping has negativeenvironmental and aesthetic consequences. As a result, authorities oftencriminalize illegal dumping and levy high fines from violators who arefound to illegally dump solid waste. Usually, authorities are only ableto prosecute offenders who are witnessed “red-handed” while illegallydumping. Enforcement of laws associated with illegal dumping isdifficult because enforcement officials are frequently not present atthe times and places where citizens illegally dump waste. There remainsa difficulty in associating solid waste found in areas in which dumpingis prohibited, with the perpetrator of illegal dumping.

There is therefore a need in the art for a marking technique suitablefor use in marking and identification of objects/materials, such assolid waste in a manner allowing in-situ detection of the markersignature marking the objects/materials, in the place at which they arelocated (e.g. in the field outdoors, without carrying a sample of theobject to be examined to a specialized lab).

However, reliable and accurate identification of XRF markers byconventional X-ray fluorescence (XRF) marking techniques requiresobtaining XRF signals with relatively high signal to noise ratio (SNR)and/or with relatively high signal to clutter ratio (SCR) which mayoften not be available when attempting to measure XRF signals in-situ,in field conditions, by utilizing portable XRF detection/measurementdevices. This is due to several reasons, among them being:

-   -   Since this XRF signal is a secondary fluorescence signal        (relatively weak), high power X-ray/Gamma-ray radiation emitters        may be required to obtain the XRF signal with SNR/SCR sufficient        for use with conventional techniques, while such high power        X-ray/Gamma-ray radiation emitters may not be available and/or        may not be suitable for use outdoors and/or with portable        devices without proper protection;    -   When operating in-situ and without vacuum conditions, the XRF        signal from the examined object may suffer significant        attenuation when it passes through the air between the examined        object and the detector, thus impairing the SNR of the        measurement;    -   Back scattering of primary radiation from the examined object        and/or objects in its vicinity, as well as interfering signals        from neighboring peaks and/or unwanted XRF response from        contaminating materials/objects (e.g. other foreign/waste        materials) located in the vicinity (e.g. at/on) the examined        objects may produce significant clutter, deteriorating the SCR        of the measurement;    -   Size and weight limitation of a portable XRF system may restrict        use of accurate X-Ray detectors/spectrometers, and might permit        use of relatively small and light X-Ray detectors/spectrometers        associated with higher internal noise (e.g.        electronic/instrumental noise of the detection device) and/or        low spectral resolution affecting the SNR of the measurement;        Thus for some or all of the above reasons, and possibly also for        other reasons, current techniques for reading XRF marking        reliably and accurately are typically performed in controlled        environments (e.g. laboratories and/or other suitable        facilities/systems).

The present invention provides a novel technique for reading XRFmarkings of objects (e.g. solid-materials but not only) with improvedaccuracy and reliably. The technique of the invention facilitates use ofhandheld/portable XRF readers for reading XRF markings of objects inun-controlled environments (e.g. in-situ, where the object to beexamined is found/located). More specifically, certain embodiments ofthe present invention provide a novel XRF signal processor and XRFsignal processing method allowing to extract an accurate XRF signature(i.e. hereinafter also indicated as fingerprint) of the examined object,even from a relatively noisy signal of deteriorated SNR and/or SCRobtained from handheld/portable XRF readers which may be operated in anun-controlled environment.

Certain aspects of the XRF signal processing technique of the inventionare based on the inventors' understanding that much of the noise andclutter appearing in a noisy XRF signal appear in the form of a trendand/or periodic components appearing in the wavelength spectrum profileof the signal, and that application of proper filtration to remove suchcomponents may yield a filtered spectral profile at which the XRFsignature appears with significantly higher SNR/SCR. To this end,certain embodiments of the present invention provide a novel XRF signalprocessor and XRF signal processing method, which utilize time seriesprocessing methods, such as Auto-Regressive (AR) and Moving Average (MA)techniques to filter the spectral profile of the XRF signal. As will beappreciated from the description below, the present invention alsoprovides specific AR models and/or MA models, such as and AutoRegressive Integrated Moving Average (ARIMA) model specifically designedfor filtering XRF signals. Also certain embodiments provide methods,based on the Box-Jenkins and/or Seasonal-Decomposition approaches forapplying the Auto Regressive models and/or Moving Average models tofilter the wavelength spectra of an XRF signal. Indeed AR and MA models,such as ARIMA, as well as Box-Jenkins and Seasonal-Decomposition, aregenerally time series analysis statistical techniques which areconventionally used for analyzing time series data typically consistingof successive measurements made over a time interval. Yet, surprisinglythe inventors of the present invention have found that application ofthese techniques (e.g. with proper adjustments often arrived at viatrial and error), to filtration of the wavelength spectrum of XRF, allprovide comprehensive results in filtering out noise and/or clutter fromXRF signals.

It should be noted that here and in the following, the phraseuncontrolled environment should be understood as any environment such asoutdoors, where the XRF signal propagates to the detector through theambient media/air without vacuum conditions and where contaminatingobjects/material which may reside near/on the examined material are notnecessarily removed away before the examination. It should also be notedthat the terms handheld and portable when used herein in the context ofthe XRF device indicate a device that can be configured to be carried bypersonnel and which is operable in situ to perform the XRF reading.

Thus in certain embodiments the XRF signal processor and/or XRF signalprocessing method of the present invention are used to accuratelyextract XRF signatures from a noisy XRF signal. As indicated above, theprocessing method/system of the invention may be used for processing XRFsignals obtained by handheld/portable XRF readers. Accordingly, certainaspects of the present invention are directed to a novel XRF deviceincorporating the XRF signal processor and/or XRF signal processingmethod of the present invention. Certain embodiments of the presentinvention also provide a novel handheld/portable XRF device configuredto include the XRF signal processor of the invention and/or to be incommunication with the XRF signal processor (e.g. possibly residing at aprocessing center) of the invention and adapted for operating the XRFsignal processor to filter the spectrum of the XRF signal read by thehandheld/portable XRF device and extract an XRF signature therefrom.

The technique of the invention facilitates use of handheld/portable XRFreaders for reading XRF markings of objects in un-controlledenvironments (e.g. in-situ where the object to be examined isfound/located). More specifically, certain embodiments of the presentinvention provide a novel solution, allowing to extract an accurate XRFsignature (i.e. hereinafter also indicated as fingerprint) of theexamined object, even from a relatively noisy signal of deteriorated SNRand/or SCR obtained from handheld/portable XRF readers which may beoperated in un-controlled environments.

Thus, according to a broad aspect of the present invention there isprovided a method for authenticating an object marked with XRF marking.The method includes: (i) filtering a wavelength spectral profile of adetected portion of an X-Ray signal arriving from an object in responseto X-Ray or Gamma-Ray radiation applied to the object to suppress trendand periodic components from the wavelength spectral profile and therebyobtaining a filtered profile; and (ii) identifying one or more peaks inthe filtered profiled satisfying a predetermined condition therebyenabling utilizing wavelengths of the one or more peaks to identifysignatures of materials included in the object.

In some embodiments the method of the invention also includesirradiating the object with the X-Ray or Gamma-Ray radiation; detectinga portion of an X-Ray signal arriving from the object in response to theradiation applied to the object; and applying spectral processing to thedetected X-Ray signal to obtain data indicative of wavelength spectralprofile thereof within a certain X-Ray band.

According to some embodiments the filtering is carried out forwavelength spectral profiles that are associated with a plurality ofportions of the X-Ray signal arriving from the object in a plurality oftime frame portions of the X-Ray signal detected during a plurality oftime frames. Then obtaining the filtered profile is achieved bycomputing an average of a plurality of filtered spectral profilesobtained by the filtering of the plurality of portions of the X-Raysignal that are obtained for the plurality of time frames.

According to some embodiments of the invention the wavelengths andpossibly also the magnitudes of the one or more peaks are used todetermine material data indicative of types and possibly alsoconcentrations of materials included in the object. The material data isthen utilized to authenticate the object.

According to some embodiments of the invention the filtering isperformed by applying a time series analysis technique to the wavelengthspectral profile of the detected signal portion to suppress said trendand periodic components from the wavelength spectral profile. The trendand periodic components, that are suppressed by the filtering, areassociated with at least one of clutter and noise appearing in thedetected portion of the X-Ray signal and sourced from one or more of thefollowing: instrumental noise of the detection device, one or moreforeign materials in the vicinity of the object, back-scattering noise,and interfering signals from neighboring peaks; said filtering therebyprovides for improved Signal to Noise ratio (SNR).

In some embodiments the filtering includes providing a predeterminedAuto-Regressive (AR) model for filtering spectra of XRF signals. Forinstance the predetermined Auto-Regressive (AR) model may be anAuto-Regressive-Integrated-Moving-Average (ARIMA) model. TheAuto-Regressive and Moving-Average orders of the ARIMA model may be p=5and q=12 respectively. Alternatively or additionally the Auto-Regressiveweights of the ARIMA model may be determined based on an autocorrelationfunction of the wavelength spectral profile.

Also in some embodiments the filtering is performed by applying at leastone of: Box-Jenkins processing and Seasonal-Decomposition processing tosaid portion of the detected X-Ray signal. For example the filtering mayinclude seasonality filtration applied for suppressing the periodiccomponent, and/or stationarity filtration applied for suppressing thetrend component.

According to another broad aspect of the invention there is provided anX-Ray Fluorescence (XRF) device comprising a processor adapted forobtaining data indicative of a wavelength spectral profile of the X-Raysignal portion arriving from an object in response to irradiation ofsaid object by X-Ray or Gamma-Ray radiation and detected by a radiationdetector, and processing the wavelength spectral profile to identifysignatures of materials included in the object. The processor includes afiltration module adapted for filtering said wavelength spectral profileto suppress trend components and periodic components from the wavelengthspectral profile, wherein the trend components and periodic componentsare associated with at least one of noise and clutter in the X-Raysignal portion detected by said radiation detector. The processorthereby provides for obtaining a filtered profile with improved signalto noise and/or signal to clutter ratio from which spectral peaksassociated with signatures of materials included in the object can beidentified with improved accuracy and reliability.

Embodiments of the invention also provide methods for marking materials,preferably using a marker or markers which can be identified using X-rayfluorescence (XRF). The markers may be easily applied to materials, in aspecific detectable quantity. Optionally, the marker comprises acomposition comprising a marker compound comprising an atom that isdetectable using XRF. The markers may be coded to provide a unique XRFsignature (“fingerprint”) which enables formation of a database whichassociates marked materials with appropriate manufacturers, batchnumbers, manufacturing date, manufacturing site, serial numbers,customer data, port of origin, port of destination and other datarelevant to the supply chain and/or the product. The marking may not beexternally visible and may be detected using an XRF detector, preferablyby a handheld/portable XRF detector. The detector may be configured tocommunicate with a server in order to provide indication ofauthentication of the material.

Embodiments of the invention provide methods for marking wastematerials, such as solid waste materials, or materials which potentiallywill require disposal. Marking waste materials may be performed usingmarkers which can be identified using XRF. The markers may be easilyapplied to waste materials, before the material is disposed, by arelevant party, such as a municipality, and may stay adhered to orabsorbed by the waste materials after the waste materials are dumped.The markers may be coded to provide a unique “fingerprint” which enablesauthorities to form a database that associates marked waste materials orpotential waste materials, with entities (people or organizations)responsible for proper disposal of the waste.

Upon finding illegally disposed waste, an authority or an agent thereofmay scan the waste for presence of a marker. Upon identification of amarker, the marker may be correlated to the identity of the entityresponsible for proper disposal of the waste.

According to an embodiment of the invention, a method is provided formarking a solid waste material, comprising obtaining a material that canbe identified using X-ray fluorescence, admixing the material with aliquid carrier to form a marking composition, and contacting the solidwaste material with the marking composition.

Further embodiments of the invention provide methods for identifying anentity responsible for disposal of materials/objects such as solidwaste. The method comprises: providing data indicative of unique XRFsignatures of XRF markers used for marking materials/objects (e.g. solidmaterial), which will potentially require disposal; providingassociation data that associates an entity responsible for disposal ofthe materials/objects/solid waste with the XRF signature of a marker orplurality of markers used for marking them (e.g. the association datamay be stored in a database); receiving measurement data indicative oftesting of a sample/portion of the solid waste material for presence ofan XRF marker or a plurality of XRF markers; processing the measurementdata to identify an XRF signature of the XRF marker or plurality of XRFmarkers, and using the association data (e.g. by querying the databaseat which it is stored) to identify the entity responsible for disposalof the solid waste material.

In the discussion, unless otherwise stated, adjectives such as“substantially” and “about” modifying a condition or relationshipcharacteristic of a feature or features of an embodiment of theinvention, are understood to mean that the condition or characteristicis defined to within tolerances that are acceptable for operation of theembodiment for an application for which it is intended. Unless otherwiseindicated, the word “or” in the specification and claims is consideredto be the inclusive “or” rather than the exclusive or, and indicates atleast one of, or any combination of, items it conjoins.

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify key features oressential features of the claimed subject matter, nor is it intended tobe used to limit the scope of the claimed subject matter.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to better understand the subject matter that is disclosedherein and to exemplify how it may be carried out in practice,embodiments will now be described, by way of non-limiting example only,with reference to the accompanying drawings, in which:

FIGS. 1A to 1C illustrate schematically the technique for reading XRFmarkings according to certain embodiments of the present invention,wherein: FIG. 1A is a flow diagram of a method 100 for reading XRFmarkings, FIG. 1B shows schematic graphs illustrating components of anXRF signal being filtered according to the method 100 illustrated inFIG. 1A; FIG. 1C depicts graphs exemplifying an XRF signals A1 and A2before and after it has being filtered by the method 100 respectively;

FIGS. 2A to 2C exemplify an XRF signal processing technique forfiltering an XRF signal according to certain embodiments of the presentinvention, wherein: FIG. 2A shows a flow diagram of an XRF signalprocessing method 200 used in certain embodiments for filtering an XRFsignal to extract therefrom an XRF signature with improved SNR and/orimproved SCR; and FIGS. 2B and 2C are graphs exemplifying the operationof method 200 illustrated in FIG. 2A;

FIG. 3 is a block diagram of an XRF device comprising an XRF signalprocessor configured according to an embodiment of the presentinvention;

FIGS. 4A and 4B are block diagrams respectively exemplifying theconfigurations of a processing center XRF device and a mobile (e.g.handheld) XRF device according to embodiments of the present invention;

FIG. 5 shows a flow diagram depicting a process according to embodimentsof the invention;

FIG. 6 shows a flow diagram depicting a process according to embodimentsof the invention;

FIG. 7 shows a flow diagram depicting a process according to embodimentsof the invention; and

FIG. 8 depicts a system which may be used according to embodiments ofthe invention for analysis of material and/or analysis of waste anddetermination of its source.

Dimensions of components and features shown in the figures are chosenfor convenience and clarity of presentation and are not necessarilyshown to scale.

DETAILED DESCRIPTION OF EMBODIMENTS

In the following detailed description, novel methods for marking andidentifying objects/materials such as solid waste will be described indetail.

Reference is now made to FIG. 1A, which shows a flow-diagram depicting amethod 100 for method 100 for reading XRF markings according to certainembodiments of the present invention. The method 100 provides a noveltechnique for reading XRF markings of an object under examination toallow identification and/or authentication and/or determination ofcertain properties associated with the object based on the XRF markingof the object. Method 100 allows extraction of an XRF signature of theobject from a noisy XRF signal with improved SNR and improved SCRthereby facilitates in-situ examination of objects and/or material viamobile (portable/handheld) devices. Method 100 includes at leastoperations 120, 130 and 150 for filtering a wavelength spectral profileof an XRF signal, which is obtained/detected in response to X-Ray and/orGamma-Ray radiation applied to the object, by utilizing statistical timeseries techniques to remove/suppress trend components and/or periodiccomponents, and preferably both, from the wavelength spectral profileand identifying an XRF signature of the object from the filtered signal.

Optional operation 105 of method 100 includes irradiating an object tobe examined by an X-Ray or Gamma-Ray radiation to excite XRF responsefrom the object. It should be understood that various techniques may beused in operation 105 for irradiating the object with X-Ray/Gamma-Rayradiation, and may vary in different implementations of the method ofthe invention. A person versed in the art would readily appreciate typesof radiation emitters, as well as the wavelength band and/or intensityof the radiation to be used usable given the requirements and conditionsat which reading of XRF marking is required in the differentimplementations. For instance, the radiation emitter used should beoperable for emitting X-Ray radiation with energy higher than the“energy” of the atoms/elements that form part of the XRF-marking andtherefore need to be identified. Optionally, operation 105 includesapplication of precaution/safety measures before the irradiating theobject to be examined by X-Ray or Gamma-Ray. For instance in someembodiments of the invention the XRF device includes a proximity/touchsensor which prevents activation of the radiation source/emitter unlessa sample/part of the object to be examined is placed adjacent to theemitter (e.g. blocking the propagation path of the radiation).

Optional operation 110 of method 100 includes detecting and spectrallyprocessing at least a portion of an XRF signal arriving from an objectin response to X-Ray or Gamma-Ray radiation applied thereto. The XRFsignal may be for example detected by detectors and/or spectrometersoperable in a desired X-Ray band. The detected portion of the XRF signalis processed by utilizing suitable spectral processing techniques, suchas a multichannel analyzer to determine the wavelength spectral profilethereof.

It should be noted that operations 105 and 110 are optional operationswhich are not necessarily carried out in all systems/devicesimplementing the method 100 of the invention. For example, some systems,implemented as central XRF signal processing systems, may be adapted forreceiving data indicative of the spectral profile of the detected signalportion from an external XRF measurement unit/module implementing theoperations of irradiating the examined object and/or detecting the XRFresponse. Also mobile XRF readers configured according to the presentinvention may be configured for detecting XRF signals arriving inresponse to X-/Gamma-ray radiation applied to the examined object by aseparate radiation source module, and therefore such mobile XRF readersmight not implement the operation 105 of irradiating the object.

To this end, in operation 120 data indicative of a wavelength spectralprofile of at least a portion of the detected XRF signal, after it hasbeen spectrally analyzed, is provided for processing according to thetechnique of the present invention to identify the XRF signaturetherein.

Operation 130 includes filtering the wavelength spectral profile tosuppress trend and/or periodic components appearing therein and obtain afiltered profile. An advantage of the present invention relates to thenovel filtering technique for filtering an XRF spectral profile which isdescribed in the following in relation to this and the next operationsof method 100, and also exemplified in details below with reference toFIGS. 2A to 2H. According to the invention significant parts of thenoise and clutter in the detected XRF signal are distributed withidentifiable characteristics within the wavelength spectral profile ofthe XRF signal. Particularly, significant portions of the noise andclutter appear in the form of trend and/or of periodic components withinthe wavelength spectral profile, which have characterizing featuresenabling to detect and suppress them from the wavelength spectralprofile.

This is illustrated for example in FIG. 1B which shows schematicspectral graphs (intensity in arbitrary units as function ofwavelengths) of different components of the wavelength spectral profileof the XRF signal, wherein:

G1—is a graph illustrating a section of a wavelength spectral profile ofan XRF signal that is obtained from the detector. As shown here, theintensity of the XRF signal varies in scale between 50 and 100 inarbitrary units.

G2—is a graph illustrating a periodic component of the wavelengthspectral profile, which has a certain periodicity. This periodiccomponent may be associated for exampled with noise/clutter, such aselectronic noise and/or back scattering. It is noted that the magnitudeof the intensity of the periodic component that is illustrated in thisgraph varies between −10 and 10 in the same arbitrary units as in theabove graph.

G3—is a graph illustrating a trend component of the wavelength spectralprofile, which shows the tendency of the intensity of the XRF signal torise/descend as a function of the wavelength. This trend component maybe associated for example with noise/clutter. It is noted that theintensity of the trend component almost monotonically rises in thisexample from 50 to 95 in the same arbitrary units as in the abovegraphs.

G4—is a graph illustrating a filtered profile obtainable by applyingoperation 130 to suppress the periodic and trend components shown in G2and G3 from the wavelength spectral profile of the XRF signal shown inG1. As shown here, subtracting/differentiating the trend components (G3)and the periodic components (G2) from the wavelength spectral profile(G1), provides a filtered spectral profile in which the spectral linesof the XRF signature appear more clearly and are not, or are lessobscured by the trend and periodic components which are associated withnoise. It should be noted that the intensity of the spectral lines ofthe XRF signature in the present example is a scale of between 0 to 4(in the same arbitrary units used above) thus being in this example anorder of magnitude lower from the trend component and also much lowerfrom the periodic component.

In view of the above, it is clear that the XRF signature in the XRFsignal of G1 is completely obscured by the periodic and trend componentsG3 and G2 (which are mostly with noise/clutter). Therefore, to be ableto read the XRF signature from such an XRF signal without suppressingthese components requires using higher intensity X-Ray/Gamma-Rayemitters, more accurate and less noisy detectors, and/or conducting themeasurement in less noisy conditions providing reduced clutter. Thetechnique of the present invention provides for solving these problemsby removing the trend and periodic components from the XRF signal. Evenmore specifically, as described in more detail below, the presentinvention also provides a novel technique identifying and filteringthese noise components for removing the periodic and/or the trendcomponents by utilizing statistical techniques which are borrowed fromfield of time-series statistical analyses and which are conventionallyused to time sequences. For instance, in certain embodiments of thepresent invention, in operation 130 predetermined models such asauto-regressive models and/or moving average models (e.g. ARIMA) areprovided and used to identify/filter the periodic and/or trendcomponents of the wavelength spectral profile of the XRF signal.

As indicated above, ARIMA models (generally referred to as anARIMA(p,d,q) where parameters p, d, and q are non-negative integers thatrefer to the order of the autoregressive, integrated, and moving averageparts of the model respectively) are conventionally used in statisticalprocessing of time series to better understand the data, or to predictfuture points in the time series. Here the ARIMA model is used toprocess the wavelength spectrum of the XRF signal, and the parameters ofthe model, p, d and q, are selected to filter out trend and/or periodiccomponents from the XRF signal. In some embodiments of the invention theparameters of the model, p, d and q, are specificallyselected/determined for filtration of the wavelength spectral profile ofthe XRF signal. The parameters may be determined (e.g. predetermined inadvance for example by trial and error and/or by computer simulations),so that they fit extraction/filtration of periodic and/or trend(noise/clutter) spectral components of the XRF signal. Also, in certainembodiments of the present invention, in operation 130 time seriesmethods, such as Box-Jenkins and/or Seasonal Decomposition methodsand/or variants of such methods, are used for filtering the XRF signalto suppress the periodic and/or trend spectral components from thesignal. For example, the Box-Jenkins and/or Seasonal Decompositionmethods may be applied for processing the wavelength spectrum of the XRFsignal based on a selected ARIMA model to thereby obtain a filteredspectral profile of the XRF signal from which the XRF signature can beextracted. FIG. 1C depicts graphs A1 and A2 of an actual XRF signalrespectively before and after it was filtered by method 100. An exampleof an implementation of method 100 is described in detail withreferences to the flow diagram of FIG. 2A.

In this regard it should be noted that the fact that noise and clutterin the XRF signal are expressed in the form of periodic and/or trendcomponents in the wavelength spectra of XRF signal, is surprising andwould not be obvious to a person of ordinary skill in the art.Accordingly, also the use of time series techniques to identify and/orfilter the trend component (also referred to herein as non-stationary)and/or the periodic component components (also referred to herein asseasonality component) from the spectra would not be obvious to a personof ordinary skill in the art.

It is noted that, in the time-series statistical analysis field, thetrend and periodic components of the time series are often referred toas non-stationary and seasonal components respectively; accordingly,these terms are also used interchangeably herein to respectivelyindicate the trend and periodic components of the spectrum, even thoughthese trend and periodic components of the spectra present trend and/orperiodicity with respect to the wavelength scale and not the time scale.

Optionally, in some embodiments operation 140 is carried out in order tofurther improve accuracy and reliability of the XRF signature which issubsequently obtained in operation 150 described in the following. Theoptional operation 140 includes repetitions of the above describedoperations 120 to 130 for filtering the wavelength spectral profiles ofa plurality of X-Ray signal portions, which arrive from the object in aplurality of time frames. The final filtered profile of the XRF signalis then computed by integrating (e.g. summing/averaging) the filteredprofiles obtained in operations 130 by filtering the wavelength spectraof the respective plurality of time frames. In this way the SCR/SNR inthe final filtered profile is further improved as compared to a filteredprofile of a single time frame, thereby enabling to obtain the XRFsignature with improved reliability and accuracy.

In operation 150, data indicative of the XRF-signature of the object isobtained from the filtered profile obtained in operation 130 or inoptional operation 140 (e.g. the final filtered profile). Operation 150includes identifying peaks in the filtered profile which satisfy apredetermined condition(s) and utilizing those peaks to determine theXRF signature of the examined object.

For instance, in some embodiments of the present invention thepredetermined conditions include identifying peaks, whose max intensityand/or slop exceeds certain predetermined threshold(s). In this case, in150, peaks whose intensity/slop is below the threshold(s) are ignoredand the remaining wavelengths, and possibly also the intensities of theremaining peaks, whose height/slop is above the threshold(s) are used toprovide data indicative of the XRF signature.

Alternatively or additionally, in certain embodiments the predeterminedconditions are based on the XRF spectral response of predetermined setof reference materials which are considered as part of the XRF-markingof the object. Reference data, such as a lookup table (LUT), indicativeof the reference spectral responses of one or more different referencematerials, may be stored in a memory. For example for each referencematerial the reference data may include wavelengths of one or morespectral peaks that are generally included in the spectral XRF responseof the material, and possibly also the relative height of those peaks(the heights in the reference data may be normalized to a certain scale(e.g. to a certain concentration of the reference materials). In suchembodiments operation 150 includes processing the filtered profile basedon the reference data to determine correlation values indicative of thedegrees of correlation between the reference spectral responses of thereference materials, with the filtered profile. The correlation valuesmay serve, and/or may be used to determine the data indicative of, theXRF signature of the examined object and may actually be indicative ofthe concentrations of the reference materials in the examined object.

The wavelengths and magnitudes of the one or more peaks are used in 150to determine XRF signature data indicative of types and/orconcentrations of XRF marking materials included the object. The typesand/or concentrations of the XRF marking materials (namely the XRFsignature data) can further be used to identify and/or authenticate theobject.

To this end, the object may be marked by an XRF-marking compound(hereinafter referred to also as XRF-marker and/or marker compoundand/or marker) detectable using X-ray fluorescence. Optionally, themarker compound may be a substituted alkane, in which at least onehydrogen atom is substituted by an element which can be detected by anX-ray fluorescence analyzer (XRF). The resultant compound may have ageneral formula CnH2n+2−mXm, wherein n=1, 2, 3 . . . , and m=1, 2, 3 . .. “X” is any element which can be detected by an X-ray fluorescenceanalyzer (XRF). For example, X may be lithium (Li), an alkali metal,which forms one covalent bond with a carbon atom.

According to another example the marker can be a halogenic compound,such as an alkyl halide having the general formula CnH2n+2−mXm, wheren=1, 2, 3 . . . , m=1, 2, 3 . . . “X” is a halogen such as fluorine (F),chlorine (Cl), bromine (Br), and iodine (I). An example of such an alkylhalide is tetrabromoethane having the molecular formula C2H2Br4. Themarker may also be an aryl halide having the general formula C6H6-mXmwherein m=1, 2, 3, 4, 5 or 6, and “X” is a halogen such as fluorine (F),chlorine (Cl), bromine (Br), and iodine (I).

Optionally, the marker compound may be an alkyl or aryl halide selectedfrom the group consisting of: 1,1,2,2 tetrachloroethane (i.e., C2H2Cl4),1,1,2 trichloroethane (i.e., C2H3Cl3), pentachloroethane (i.e., C2HCl5),hexachloroethane (i.e., C2Cl6), 1,2,4 trichlorobenzene (i.e., C6H3Cl3),1,2,4,5 tetrachlorobenzene (i.e., C6H2Cl4), ethyliodide (i.e., C2H5I),ethylbromide (i.e., C2H5Br), dichloro 1,2 dibromoethane (i.e.,C2H2Cl2Br2), dichlorotribromoethane (i.e., C2HCl2Br3),difluoro-1-chloroethane (i.e., C2H3F2Cl), difluoro 1,2 dibromoethane(i.e., C2H2F2Br2), trifluoro 1,2,2 dibromoethane (i.e., C2HF3Br2),tribromopropane (i.e., C3H5Br3), dibromobenzene (i.e., C6H4Br2),dibromoethane (i.e., C2H4Br4), n-propylbromide (i.e., C3H7Br),parabromofluorobenzene (i.e., C6H4FBr) butylbromide (i.e., C4H9Br) andoctylbromide (i.e., C8H17Br).

According to another example, the marker can be an organometallic or ahalogenic compound in which at least one metallic element or at leastone halogen, bonds with at least one carbon atom of an alkene (olefine),having the general formula CnH2n−mXm, where n=1, 2, 3 . . . , m=1, 2, 3. . . “X” is either an alkali metal or a halogen. An example of such acompound is bromoethylene having the molecular formula C2H3Br.

According to a further example, the marker can be any of the abovementioned compounds wherein silicon (Si), germanium (Ge), and the like,substitute an atom of carbon. For example, diethyl silane (i.e.,C4H12Si) is such a compound. It will be noted that silicon is detectableby the X-ray fluorescence analyzer and no substitutions for hydrogenatoms are necessary. Accordingly, “X” elements do not need to appear inthe compound, if the silicon, germanium or other element serve as themarking element detectable by the X-ray fluorescence analyzer. Foralkanes, the general formula of the compound is Cn−mH2n+2Ym, where n=1,2, 3 . . . , m=1, 2, 3 . . . , m<n and where “Y” designates the silicon,germanium or other element. For alkenes (olefines), the general formulaof the compound is Cn−mH2nYm, where n=1, 2, 3 . . . , m=1, 2, 3 . . .and where “Y” designates the silicon, germanium or other element.

According to an embodiment of the invention, the marker comprises a saltcomprising an atom having an atomic number comparable to lithium, orhigher. According to an embodiment of the invention, the markercomprises a salt comprising an atom having an atomic number comparableto magnesium, or higher

In some embodiments detectable compositions usable for marking theobject by XRF-markers are formed by admixing an XRF-marker compound witha carrier. The detectable composition may be in liquid form. Preferably,the composition comprises an agent that assists in the adhering of thecomposition to the material to be marked, or an agent which assists inthe absorption of the composition in the material to be marked. Theagent, according to an embodiment of invention, may be a binder. Thebinder may comprise one or a combination of: alkyds, acrylics,vinyl-acrylics, vinyl acetate/ethylene (VAE), polyurethanes, polyesters,melamine resins, epoxy, or oils. Detectable compositions may furthercomprise a pigment and/or a solvent. For example detectable compositionsmay be in the form of a paint, glue or epoxy.

To this end, the reference data used in 150 may include data indicativeof various detectable compositions and/or markers which are used by thetechnique of the present invention to mark and identify objects. In someembodiments, the technique of the invention enables detection ofXRF-markers, which present in the object in concentrations in the rangeof between about 100 parts per billion (ppb) to 100 parts per million(ppm).

FIG. 2A is a flow chart illustrating in more detail a method 200 forprocessing XRF signals according to certain embodiments of the presentinvention. The method includes operations 220, 230 and optionaloperation 240, in which: in operation 220, data/signals indicative of awavelength spectral profile of at least a portion of a detected XRFsignal is provided, in 230 the wavelength spectral profile the portionof the detected XRF signal is filtered to suppress trend and periodiccomponents, and optional operation 240 includes repetitions ofoperations 220 and 230 for filtering the wavelengths spectral profilesof a plurality X-Ray signal portions, which arrive from the object in aplurality of time frames, and integration (e.g. averaging of theplurality of filtered spectral profiles obtained in this way to obtain afinal filtered profile with improved SNR and/or improved SCR).Operations 220 and 240 are generally similar to operations 120 and 140described above and therefore need not be described in the following inmore detail. Operation 230 of method 200 is a particular example of animplementation of operation 130 of method 100 described above.

Operation 230 includes sub operation 232 for providing anAuto-Regressive (AR) model for filtering the wavelength spectral profileprovided in 220. As indicated in 232.1, optionally the model used is anARIMA model. The parameters of the model are obtained for filtering theXRF signal. The parameters may be predetermined parameters previouslydetermined to fit filtration of an XRF signal (e.g. stored in memory)and/or, optionally, in 232.2 certain of the parameters may be determinedbased on the wavelength spectral profile which is to be filtered. Forexample the autoregressive parameter p, may be determined (e.g.dynamically determined in real time) by calculating the autocorrelationfunction of the wavelength spectral profile and identifying thelocation(s) of extremums (e.g. maxima) in the autocorrelation function.

For instance in some embodiments the Auto Regressive P, Integration d,and Moving Average q parameter/orders of the ARIMA model are set asfollow: p=5 and q=12. In certain embodiments q consecutive MovingAverage (MA) weights selected from the repeated series of weights areused for the MA part of the ARIMA model. The inventors of the presentinvention have realized that in some cases using this set of MA weightsprovides good results when filtering XRF wavelength spectra.

Operation 230 includes sub operation 234 in which the wavelengthspectral profile is filtered the based on the AR (e.g. ARIMA) model byutilizing time-series processing techniques, being an adaptation of theBox-Jenkins and Seasonal-Decomposition processing techniques tofiltration of the XRF-signal.

For instance, in optional sub operation 234.1 seasonality filtration isapplied to suppress the periodic component from the wavelength spectralprofile. In this example, seasonality filtration may include:

a.—applying moving average to the wavelength spectral profile to obtaina smoothed profile of the wavelength spectral profile. An example of awavelength spectral profile of an XRF signal that is provided in 220 isillustrated in FIG. 2B. In this example, the moving average is appliedby averaging q=12 consecutive samples of the XRF signal with q=12weights that are given in the ARIMA model provided in sub operation 232.

b.—then, the smoothed profile is differentiated, in this case bysubtraction of the smoothed profile from the wavelength spectral profileP1 to obtain a seasonality profile indicative of the periodic peakswhich are associated with noise and/or clutter and which exist in thewavelength spectral profile P1. It should be noted that although theinventors have found that in some implementations it is preferable toperform the differentiation by subtraction of the smoothed profile fromthe wavelength spectral profile P1, yet in some embodiments thedifferentiation may be performed in another way to obtain theseasonality profile, for instance by division of the wavelength spectralprofile P1 by the smoothed profile (e.g. or vice versa).

c.—finally, in order to suppress the periodic components from thewavelength spectral profile P1 and obtain a “seasonality free”wavelength spectral profile the seasonality profile obtained in (b.) issmoothed by applying a moving average to obtain a smoothed seasonalityprofile and then differentiating the smoothed seasonality profile fromthe wavelength spectral profile P1 thereby obtaining the “seasonalityfree” wavelength spectral profile from which at least some periodiccomponents are suppressed.

In optional sub operation 234.2, stationarity filtration is applied tosuppress the trend component from the “seasonality free” wavelengthspectral profile (or from the wavelength spectral profile P1, e.g. incase steps a. to c. above were not performed). In this example thestationarity filtration includes:

d.—applying moving average to the “seasonality free” wavelength spectralprofile (e.g. this may also be applied to the wavelength spectralprofile P1) to obtain stationarity profile indicative of at least a partof the trend component existing in the wavelength spectral profile P1.

e.—Then, differencing between seasonality free spectral profile (e.g. orthe wavelength spectral profile P1) and the stationarity profile, inorder to suppress the trend component from the “seasonality free”wavelength spectral profile (e.g. or from the wavelength spectralprofile P1) and obtain a trend free spectral profile P6 in which thetrend component is suppressed. The “trend free” spectral profile P6obtained at this stage is illustrated for example in FIG. 2C. It shouldbe noted that here the differentiation is performed by subtracting thestationarity profile from the “seasonality free” wavelength spectralprofile, and that to this end the profile P6 is actually a filteredwavelength spectral profile of the XRF-signal from which bothseasonality (periodic) components and stationarity (trend) componentsare suppressed. It should also be understood that although thedifferentiation of this step is performed in this example bysubtraction, in some embodiments the differentiation to remove the trendcomponent may be performed by other techniques, for example by divisionof the “seasonality free” wavelength spectral profile (e.g. or from thewavelength spectral profile P1) by the stationarity profile.

Thus, at the end of operation 234 exemplified above a filteredwavelength spectral profile P6 is obtained from which significant partsof both the trend and the periodic components, which are associated withnoise/clutter, are removed. Remaining prominent peaks are mainlyindicative of the actual XRF signature of the examined object. In thefollowing operation similarly 150 described above may be performed toextract data indicative of the XRF signature from the filtered profileP6 with improved accuracy and reliability.

Comparing the spectral profiles P1 and P6, before and after filtrationby the technique of the present invention, it is noted that much of thenoise and clutter is suppressed in profile P6. In the profile P6 afterfiltration, peaks in the area of 850 along the y-axis are visible. Thesensitivity is improved as can be seen by comparing the scale of theY-axis of FIG. 2B, which is in the range of about 0-80, and the scale ofthe Y-axis of FIG. 2C, which is around the range of 0-2. This increasedsensitivity allows for user of smaller amounts of marking substances, aspeak resolution is increased.

Turning now to FIG. 3, a block diagram exemplifying an X-RayFluorescence (XRF) device 300 configured according to some embodimentsof the present invention is exemplified. The XRF device 300 includes anXRF Spectral Data/Signal provider 320 that is adapted to provide dataindicative of a wavelength spectral profile of an XRF signal portionthat arrived from an object in response to irradiation of the object byX-Ray or Gamma-Ray radiation and detection of the response XRF signal bya radiation detector. The XRF device 300 also includes an XRF-markingreading processor 310 (hereinafter ‘processor’) that is adapted processthe wavelength spectral profile in accordance with the technique of thepresent invention (e.g. implementing method 100 and/or method 200described above) to a filtered profile indicative of the XRF signaturesof materials (e.g. XRF markers) included in the object. The XRF device300 also includes an identification module 330 adapted to process thefiltered profile to identify the XRF signature therein and provide dataindicative thereof. The identification module 330 may be adapted, forexample, to carry out the operation 150 of method 100 described above toidentify, in the filtered profile, peaks satisfying a predeterminedcriteria, and utilizing the wavelengths, and possibly also themagnitudes of those peaks, to identify the XRF signature of the object.Also the device 300 may also include an XRF Marking Data Retriever 340associated with a memory storing reference data indicative of variousdetectable compositions and/or markers which are used to mark objects,and which may be adapted to process the data indicative of the XRFsignature obtained by identification module 330 based on the referencedata, and determining the XRF-marker used to mark the object andproviding and/or storing data indicative thereof.

According to some embodiments of the present invention the processor 310includes a filtration module 315 including at least one of a periodicityfilter 315.2 and a trend filter 315A that are respectively adapted forfiltering the wavelength spectral profile to suppress periodiccomponents and trend components therefrom. For example in someembodiments the filtration module 315 includes a periodicity filter315.2 and a trend filter 315.4 that are respectively configured andoperable for implementing operations 234.1 and 234.2 described above inorder to suppress the periodic and trend components from the wavelengthspectral profile of the XRF signal portion.

According to some embodiments of the present invention the processor 310also includes a time frame segmentor 312 and a time frame integrator 317which are configured and operable for implementing method operations 140and/or 240 in order to further reduce the noise and/or clutter from thefinal filtered signal. To this end, the time frame segmentor 312 isconfigured and operable to segment the XRF signal provided by the XRFSpectral Data/Signal provider 320 into a plurality of (i.e. two or more)wavelength spectral profiles. The filtration module 315 then filterseach of the wavelength spectral profiles independently toremove/suppress the trend and/or periodic components therefrom. Then thetime frame integrator 317 integrates (e.g. averages) the filteredprofiles obtained by the filtration module for each of the signalportions of the different time frames to obtain a final filtered profilewith improved SNR and/or SCR.

It should be noted that generally the XRF device of the presentinvention may be implemented by analogue and/or digital means. In somecases the XRF device includes a computerized system including a computerprocessor (CPU) and a memory. The modules of the device may thus beimplemented by suitable circuitry and/or by software and/or hardwarecomponents including computer readable code configured for implementingthe operations of methods 100 and/or 200 described above.

The XRF device of the present invention may be implemented as part of anXRF signal processing center, and/or as a portable (e.g. handheld) XRFreading device.

An XRF device 300 of the invention implemented in an XRF signalprocessing center is illustrated in a block diagram in FIG. 4A.Description of the configuration and operation of commonelements/modules of the device 300 which are similar to those of thedevice shown in FIG. 3 will be repeated here. In the implementation ofthe XRF device of in an XRF signal processing center, the XRF SpectralData/Signal provider 320 includes and/or is associated with acommunication module 322, and is operable receiving data indicative ofthe XRF signal via communication with a remote XRF reading device whichis used to detect the XRF signal response from the object. Also in thisimplementation the XRF Marking Data Retriever 340 includes and/or isassociated with data storage (memory) 344 storing the reference datamarking data indicative of a plurality of XRF markers to be identifiedby the XRF device 300. Possibly the data storage (memory) 344 alsostores association data associating information indicative of aplurality of objects with XRF markers. Data retriever 340browses/queries the data storage 344 to determine the XRF marker thatbest fits the XRF signature obtained by the identification module 330.Optionally the data retriever 340 also browses/queries the data storage344 to determine properties of the object based on the identified XRFmarker and the association data stored in the data storage. Then dataindicative of the identified XRF marker and/or of the properties of theidentified object may be communicated (e.g. via the communication module322 and/or via a different module) to the XRF reader providing the XRFsignal.

An XRF device 300 of the invention implemented as a handheld/portableXRF reader is illustrated in a block diagram in FIG. 4B. Description ofthe configuration and operation of common elements/modules of the device300 which are similar to those of the device described above withreference to FIG. 3 will not be repeated here. In the implementation ofthe XRF device 300 as a handheld/portable device, the XRF SpectralData/Signal provider 320 may include a radiation detector 324, such asan X-Ray spectrometer adapted to detect and spectrally analyze an XRFsignal arriving from an object in response to irradiation of the objectby X-Rays or Gamma-Rays, and provide data signals indicative of thewavelengths spectral profile of the detected signal. In some embodimentsthe radiation detector 324 enables detection an XRF marker materialmarking said object and having concentration in the order of about 1 ppmor even below, in the order of about 100 s of ppb.

In some embodiments the XRF device 300 may optionally also include aradiation emitter 350 configured and operable for emitting said X-Ray orGamma-Ray radiation for irradiating an object to be examined by theportable XRF device 300. In this implementation the XRF marking dataretriever 340 may include a communication module 342 and/or a datastorage 344 which are utilized to obtain, based on the identified XRFsignature, the XRF marking data associated with the XRF marker markingthe object and/or object data indicative of the properties of theobject. For this purpose the data storage 344 may store reference dataand/or association data associating various XRF signatures with specificXRF markers and/or associating the XRF-signatures and/or various markerswith properties of the objects marked thereby. Alternatively oradditionally, the handheld device 300 may use the communication module342 (e.g. wireless communication module) to communicate data indicativeof the XRF-signature and/or the filtered profile to a processing centerand receive therefrom data indicative of the object and/or marker dataindicative of the XRF marker used for marking the object.

In some cases, the marker data obtained by the XRF marking dataretriever 340 is indicative of one or more of the following: the XRFsignature of object in its raw form; one or more additive XRF markingmaterials added to the object to mark it; and/or a carrier material usedfor adhering XRF marking materials to the object. In some cases theobject data obtained by the XRF marking data retriever 340 includes dataindicative of one or more of the following: identity of the object;identity of a product said associated with object, identity ofmanufacturer of said object; batch number of the object, manufacturingdate of the object, manufacturing site of the object and/or serialnumber of the object; and identifier of an owner of said object. In someembodiments the XRF device 300 includes a display module 390 (e.g.including a display screen and a display controller (not shown)) whichare configured and operable to obtain the marker data and/or the objectdata from the XRF marking data retriever 340 and present on the displayscreen indicia indicative of the object.

In some embodiments the XRF device 300 includes a position locator 360(e.g. GPS) configured to determine/estimate the position of the XRFdevice 300 and utilize the communication module (e.g. 342) tocommunicate data indicative of the position to the processing centertogether with the data of the filtered profile/XRF signature. In someembodiments the XRF device 300 includes an optical reader 370 (e.g.barcode/QRcode reader) configured to read an optical code, such asbarcode/QRcode) of the object and communicate the data indicative of theoptical code to the processing center together with the data of thefiltered profile.

In some embodiments the XRF device 300 also includes a memory storing aunique identification code of the XRF device 300. The XRF device 300 maybe configured to communicate the unique identification code to thecentral computer via the communication module together with the data ofthe filtered profile.

Reference is now made to FIG. 5 which shows a flow-diagram depicting amethod 500 for the marking of waste materials/objects.

Method 500 includes 520 providing/preparing a detectable composition formarking the waste materials. Optionally, the detectable compositioncomprises an XRF marker compound that comprises an atom that isdetectable using X-ray fluorescence. According to an embodiment of theinvention, the XRF marker compound is present in the detectablecomposition in an amount enabling detection by an XRF device such asdevice 300 described above. According to an embodiment of the invention,the XRF marker compound is present in the composition in an amount suchthat the concentration of the element which can be detected by an XRFdevice is present between the range of about 100 parts per billion (ppb)and 100 parts per million (ppm).

According to an embodiment of the invention, method 500 further includes530 marking waste and/or, object(s)/or solid materials which willpotentially require disposal, by the detectable composition (e.g. XRFmarker compound) provided/prepared in 520. According to an embodiment ofthe invention, marked object/materials may comprise constructionmaterials which may be or become construction waste as a result ofdestruction or renovation of roads, buildings and other man-madestructures. Such construction materials may comprise concrete, asphalt,metal, wood, insulation materials, drywall, glass, plastic and otherassociated debris. Additional embodiments of the invention also relateto liquid materials/waste. In some embodiments of the invention, themarked object/materials are not yet in waste form at the time ofmarking. For example, if a building is scheduled to be demolished, thebuilding materials that form the building may be considered solid wastematerial and may be marked with the detectable composition, beforedemolition of the building.

According to an embodiment of the invention, the detectable (e.g. by XRFmarker) composition is in the form of paint. In such embodiments in 530the objects/materials/solid waste is marked by applying/painting theobject with a detectable XRF marking composition in the form of paint(for example by spraying). Applying a detectable/XRF-marking compositionto the solid waste material in the form of paint requires immense effortto remove the detectable composition from the solid waste material,thereby discouraging removal of the composition and subsequent illegaldisposal. In some embodiments of the invention, thedetectable/XRF-marking composition is in the form of a colored paint.The colored paint may be colored a different color than theobject/material to which it is applied, thereby enabling easyidentification of marked objects/materials disposed as waste.Alternatively, in some embodiments, the colored paint may be coloredwith a color similar to the surface of the object to which it isapplied. For example, if the object is a road having white or yellowstriping, the detectable composition may be applied in a paint havingthe same color as the striping, thereby “masking” the marking and makingthe marking difficult to find and/or remove.

According to an embodiment of the invention, the detectable compositionis a stable composition which maintains its stability and its ability tobe detected through X-ray fluorescence after being applied to the wastematerial for a period of at least a year. According to an embodiment ofthe invention, the detectable composition maintains its ability to bedetected through X-ray fluorescence after being applied to the wastematerial for a period of at least 3 years.

According to an embodiment of the invention, an appropriate detectablecomposition is matched to a specific type of construction waste beingmarked. For example, if the construction waste is concrete, a sample ofnon-marked concrete is analyzed by X-ray fluorescence for detectablepresence of atoms. A result is obtained that the concrete does notcontain detectable levels of two elements, Li and Br. As a result of theanalysis, a detectable composition comprising a known amount of Li andBr is formed and is applied to the concrete construction waste.

According to an embodiment of the invention, method 500 further includesoperation 540, for associating a signature/finger-print of thedetectable composition (e.g. XRF marker), which is used for marking andobject/material with object data including properties/parameters of theobject/material such as identification of an entity responsible fordisposal of the object/material as waste. The association data betweenthe signature of the detectable composition/XRF-marker marking theobject and the object parameters may then be stored in suitable datastorage.

In order to effectively mark waste, a coding system may be used in whichdifferent relative concentrations and/or identities of marking compoundmay be associated with different entities responsible for disposal ofthe waste.

Reference is now made to FIG. 6, which shows a flow-diagram depicting amethod 600, according to an embodiment of the invention, for identifyingan entity responsible for disposal of a waste material.

According to an embodiment of the invention, method 600 includesoperation 610 which relates to identifying/analyzing a waste material.According to embodiments of the invention, the waste material may be asolid waste material, comprising construction waste. Construction wastemay comprise concrete, asphalt, metal, wood, insulation materials,drywall, glass, plastic and other associated debris. The waste materialmay be found dumped in illegal locations. Operation 610 may be carriedout by an XRF device such as that illustrated in FIG. 4B provided in theform of an XRF marker marking spectrometer. Analyzing the waste materialto identify a marking may, according to embodiments of the invention,utilize X-Ray fluorescence to identify the marking. The analysis mayinclude bombarding the waste material with electromagnetic radiation,and analyzing the wavelength and/or intensity of fluorescence patternemitted by the marking of the waste material. Based on the wavelengthand/or intensity of the emitted fluorescence pattern, the marker may bedetermined to comprise a certain concentration of a specific atomassociated with an identity of a marker composition. According to anembodiment of the invention, waste material is analyzed with a handheldXRF device, e.g. such as that shown in FIG. 4B.

According to an embodiment of the invention, method 600 furthercomprises operation 620, which relates to comparing a marking with anassociated entity. Operation 620 is carried out after a fluorescencepattern (e.g. the XRF signature of the marker) is detected. The detectedfluorescence pattern/XRF-signature may be indicative of specificrelative concentrations of specific atoms which may correlate toconcentrations of one of a plurality of markers with which waste waspreviously marked. The fluorescence pattern/XRF-signature emitted may beindicative of specific relative concentrations of specific atoms whichmay correlate to concentrations of previously applied markers. To thisend, in operation 620 the reference data (described above) stored in adatabase may be used to compare the fluorescence pattern/XRF-signatureof the detected XRF markers with the signatures/chemical-compositions ofa plurality of XRF markers previously used for marking objects andstored in the data base.

According to an embodiment of the invention, method 600 further includesoperation 630 which relates to determining the data of the object/wastematerial marked by the identified marker, for example, determiningobject data indicative of the identity of an entity that is responsiblefor disposal of the object/waste material. To this end in operation 630the association data (described above) which is stored in the data basemay be used to determine the properties/parameters of theobject/material which is marked by the marker identified in 620. Theproperty parameters of the object may include data indicative of anentity which is responsible for disposal of the object.

According to an embodiment of the invention, method 600 further includesoptional operation 640 may include automatic initiation of an initiationaction, against the entity responsible for disposal of the wastematerial. This may be for example automatic issuance of a fine to beserved to the entity responsible for disposal of the waste material,and/or automatic enlisting of the entity, which is responsible fordisposal of the waste, in a log/task-book for further handling bysuitable personnel. To this end, as indicated above, in some cases theXRF reader device of the invention includes one or more of thefollowing: a position locator (GPS), an optical/barcode reader, and amemory storing unique identification. Utilizing data provided by suchmodules, the following data parameters may be recorded whenautomatically logging/enlisting the disposal of the waste:

-   -   The entity which is responsible for the waste disposal—this, as        well as possibly other parameters of the waste, may be        determined from the association in 630;    -   The location of the waste disposal—this data may be obtained        from the GPS/position locator of the XRF device;    -   The identity of the field officer who records the disposed        waste—this data may be obtained by utilizing the unique        identification code of the XRF device;    -   Possibly additional information about the waste which may be        obtained from barcode information encoded on the waste        objects/materials and read by the optical reader of the XRF        device.

Reference is now made to FIG. 7, which shows a flow-diagram depicting amethod 700 for authenticating a material according to embodiments of theinvention.

Method 700 comprises operation 710, which comprises a material/objectfor marking. An object/material for marking may comprise any material orproduct in which there is concern for counterfeiting or supply chaindiversion of the product. The material/object for marking may comprise apackaging which may be marked according to embodiments of the invention.The material may be selected from a group consisting of: natural gas,gemstone, coins, currency bills, identification documents,identification cards, passports, auto parts, branded goods, consumergoods, plastic, paper, adhesives, paints, pigments, nylon, cotton,synthetic fibers, metals, alloys, rubber, synthetic rubber, optic fiber,silicon, cardboard, inks, and synthetic polymer. According to anembodiment of the invention, the adhesive is selected from the groupconsisting of epoxy, polymeric glue and contact glue. According to anembodiment of the invention, the consumer goods are selected from thegroup consisting of: food, beverages, alcoholic beverages, electronics,clothing, jewelry, shoes, fashion accessories, watches, software,perfume, cosmetics, pharmaceuticals and artwork.

Method 700 further comprises operation 715, which provides an XRF markercomposition comprising a marker substance and a carrier. The markersubstance compound may be any of the markers described above (such ase.g. substituted alkane and/or a halogenic compound, and/or alkyl oraryl halide, and/or an organometallic or a halogenic compound, and/or asalt comprising an atom having an atomic number comparable to lithium,or higher). According to an embodiment of the invention, the markersubstance comprises an element having an atomic number of 12 (Magnesium)and above. According to an embodiment of the invention, the markersubstance comprises a marker compound or marker atom. According to anembodiment of the invention, a detectable composition is preparedcomprising two or more marker substances. According to an embodiment ofthe invention, the two or more marker substances emit XRF at differentfrequencies.

According to an embodiment of the invention, a marker substance is addedat a concentration relative to the carrier, of between 0.1 parts permillion and 100 parts per million. According to an embodiment of theinvention, a marker substance is added at a concentration relative tothe carrier, of between 0.5 parts per million and 30 parts per million.

According to an embodiment of the invention, a detectable composition isformed in which energy of XRF radiation, emitted when irradiating thedetectable composition at a given energy, does not correspond to theenergy of XRF radiation emitted when the marked substance is irradiatedat the same energy. This ensures that non-marked substances will notemit “false-positive” signals and will be distinguishable fromcorresponding marked substances. It is also possible to use bindermaterial whose XRF response does not interfere with the XRF signal ofthe marker.

According to an embodiment of the invention, the detectable compositiondoes not interfere with the working of the marked substance. Forexample, if the marked substance is an adhesive, addition of thedetectable composition does not alter the adhesiveness of the adhesive.

According to an embodiment of the invention, the detectable compositiondoes not negatively impact the environment and is safe to handle and usefor users of the marked material.

According to an embodiment of the invention, the energy and/or intensityof the XRF radiation emitted by a detectable composition when irradiatedat a given energy is different than the energy and/or intensity of theXRF emitted by the marker substance or marker substances that thedetectable composition comprises when irradiated alone, not in thepresence of a carrier. The carrier and the marker may each contribute tothe XRF “fingerprint” of the detectable composition relative to anunmarked substance.

Atoms of specific elements present in the marker substance, the carrier,and the marked substance or any combinations thereof, may all bedetectable by XRF. When irradiated with the appropriate energy, eachelement may emit a variety of types of energy based on electronsreverting to various shells. Each shell, for example, a K-shell,L-shell, M-shell and N-shell, may each emit a specific amount of energywhich differs for each element and each shell. A combination of readingof energy levels from a marked, irradiated substance may show, whendisplayed on a graph, multiple peaks corresponding to various energylevels for each element, relating to elements in any combination ofmarker substance, carrier and the marked substance. Methods according toembodiments of the invention attribute unique XRF fingerprints topredetermined combinations of the marker substance, carrier and themarked substance. The unique XRF fingerprints obtained from analysis ofcombinations of marker substance, carrier and the marked substance, maynot be obtainable from analysis of the marker substance, carrier andmarked substance alone.

According to an embodiment of the invention, a marker substance is mixedwith a carrier. According to an embodiment of the invention, a markersubstance is chemically bound to the carrier.

Method 700 further comprises operation 720, which comprises marking amaterial with a detectable composition.

According to an embodiment of the invention, the material is marked witha detectable composition by mixing the detectable composition with thematerial to form a mixture. According to an embodiment of the invention,the mixture is a uniform mixture. If the marked material is a liquidmaterial, such as paint, the detectable composition is chosen so that itis dispersed uniformly in the liquid material and does not settle out ofthe liquid material over time.

According to an embodiment of the invention, the material is externallymarked. According to an embodiment of the invention, the material iscoated or painted with a detectable composition. According to anembodiment of the invention, a packaging of the material is marked. Thematerial may be marked at its place of manufacture.

Method 700 further comprises operation 725, which comprises recording amarking in a database. The database may be configured to provide aunique code corresponding to a detectable composition marking. Theunique code may correspond to an XRF fingerprint/signature associatedwith the detectable composition marking. Unique codes may be generatedfor each combination of marker or combination of markers. For exampleoperation 725 may include storing in the database reference dataindicative of the signature of the marking composition used for markingthe object and possibly also storing association data associatingproperties and/or identity of the object with the signature of themarking. The coding is preferably stored in a secure database withlimited access. Concentration of each marker may be varied to providemultiple options of coding. According to an embodiment of the invention,different products/objects may be marked with the same marker atconcentrations which differ from each other by about 10 ppm. Methodsaccording to embodiments of the invention are successful indistinguishing the marked objects with a confidence level of two-sigma.

The codings, and their associated fluorescence patterns may beassociated with data regarding the marked material, including, but notlimited to, identity of product, identity of manufacturers, batchnumbers, manufacturing date, manufacturing site and/or serial numbers.

The operations 730 to 755 of method 700 described in the following aregenerally performed after the marked object/material is distributed(e.g. sold) and a suspected counterfeit sample is provided/found. Thesample may be a sample of a material which appears similar to and/or islabeled similarly to a marked item.

Method 700 may further include operation 730, which comprisesirradiating the sample. The sample may be irradiated with X-Rays orGamma rays. Samples may be irradiated with energy of up to 40 keV.

According to an embodiment of the invention, the sample is irradiatedusing a handheld XRF device. According to an embodiment of theinvention, the sample is irradiated by an XRF technician who does notknow the identity of the detectable composition.

Before or after irradiating the sample, the operator of the handheld XRFdevice may input into the handheld XRF device that he requests to testauthentication of a specific material. The operator may indicate, usingtext or a serial number associated with the material, which material isbeing verified. The handheld XRF device may transmit to a centralcomputer database regarding the operator's indication of material.

According to an embodiment of the invention, the handheld XRF device maycomprise a barcode reader configured to scan a barcode, QR code or othertype of optically encoded data. The optically encoded data may then betransmitted to a central computer, indicating what type or manufacturerof material will be analyzed.

Optionally, method 700 may further include operation 735, whichcomprises detecting XRF from the irradiated sample. According to anembodiment of the invention, the detection is performed using a handheldXRF device. According to an embodiment of the invention, a silicon driftdiode detector is used for the detection. According to an embodiment ofthe invention, XRF is detected at a range of between about 2 and 30 keV.

Optionally, method 700 may further include operation 740, whichcomprises transmitting a signal encoding the XRF data received from thedetector to a central computer. The XRF data may include data regardingenergy and/or intensity of the X-ray fluorescence of the sample. The XRFdata may include data indicative of the wavelengths spectral profile ofthe XRF signal before and/or after filtration to remove the trend and/orperiodic components therefrom. The XRF data signal may be encrypted.

Transmission of the signal from the XRF device may be performed, by wayof example, through wired, wireless, telephonic or cellularcommunication, or any combination thereof.

Transmission from the XRF device to the central computer may include anidentifier signal, unique to the XRF device to identify the XRF devicefor retrieval of information. The central computer may be configured tocontinue communication with the XRF device or to transmit information tothe XRF device only upon verification of the XRF device via a uniqueidentifier signal.

Optionally, method 700 may further include operation 745, whichcomprises comparing the received XRF data to data in the database.Received XRF data may be logged in a database. Logged received XRF datamay be used for future analyses of future samples.

Optionally, method 700 may further include operation 750, whichcomprises assessing identity of a sample based on the database data.Assessing identity may be performed using a statistical analysis inwhich received XRF data is compared to database XRF data and astatistical comparison is performed. If a predetermined level ofsimilarity is shown, the XRF data is considered to be from a matchingsample.

Optionally, method 700 may further include operation 755, whichcomprises transmitting a signal from the computer to the detectordevice. The signal can comprise identification of data regarding thematerial marked, including, but not limited to, manufacturers, batchnumbers, manufacturing date, manufacturing site, and serial numbers.

Alternatively, the signal transmitted may comprise an indication of apositive reading indicating a positive identification of an authenticitem, or a negative reading indicating that the item is not authentic.The transmitted signal may be an indication that the sample does or doesnot correspond to the information inputted regarding the sample by theXRF operator.

According to an embodiment of the invention, a log of the communicationbetween the central computer and the XRF detector may be recorded in adatabase.

Reference is now made to FIG. 4, which depicts a system that may be usedaccording to embodiments of the invention for identification ofmaterials and/or for analysis of waste and determination of its source.

FIG. 8 relates to a material analysis system 800 according toembodiments of the invention. Material analysis system 800 comprises amobile XRF device/analyzer 810 capable of reading XRF signals of objectsand a central computer 840 capable of receiving data indicative of theXRF signals, and/or signature thereof, and in response retrievingdata/parameters indicative of objects marked by a corresponding XRFmarker. At least one of the central computer 840 and the XRFdevice/analyzer 810 may be configured similarly to the XRF device 300described above with reference to FIG. 3 and include an XRF-markingreading processor 310 (implemented by software and/or hardware) that canfilter the wavelength spectral profile according to the technique of theinvention described above (e.g. implementing method 100 and/or method200 described above).

Mobile XRF analyzer 810 comprises a communication module 812, aprocessor 814, a memory 816, a display 818, a radiation emitter 820, aradiation detector 822 and an antenna 824. Central computer 840comprises a communication module 842, a processor 844, and a database846 storing reference and/or association data relating to the markingsignatures with and respective properties of the objects marked thereby(e.g. the respective entities responsible for disposal of the object).

In some embodiments the material analysis system 800 is configured in acloud-based configuration and/or utilize Internet based computing sothat parts of processor 814, processor 844, database 846 and/or memory816 may reside in multiple distinct geographic locations.

The Mobile XRF device/analyzer 810 may be a handheld device. Inoperation, operator 802 may hold a handheld mobile analyzer 810 toanalyze sample/object 830 of material or waste. Upon activation of thehandheld mobile analyzer 810 the processor 814, signals to radiationemitter 820 to emit radiation (e.g. X-ray radiation). Processor 814detects a radiation fluorescence signal pattern via radiation detector822 which is emitted from marking a composition on sample 830. Processor814 may transmit data regarding the fluorescence signal pattern (such asfluorescence wavelength and or intensity) via communication module 812,via a data communication (e.g. via cellular network 860) tocommunication module 842 of the central computer 840. The processor 244of the central computer 840 may record the received data in database 846and/or may query/cross-reference the received data with data in database846 to retrieve object data about the sample/object 830 (e.g. details ofthe object and/or identify entity responsible for its disposal) and maycommunicate such object data to the mobile device at which processor 814may signal to display 818 to display a message corresponding to theobject data.

In view of the above, embodiments of the invention provide convenientmethods for marking and analysis of materials and of waste. An XRFtechnician may easily analyze materials to determine if they arecounterfeited or genuine. An environmental waste technician may easilyanalyze illegally dumped waste using a portable, hand-held machine thatmay quickly and easily identify the entity responsible for illegaldisposal of the waste.

Methods according to embodiments of the invention may be illustrated bythe examples below:

Example 1

The engineering department of the city of Haifa, Israel, is responsiblefor road works within the limits of the city. The department has offered10 tenders (numbered 1-10) for various road construction projects in thecity. All 10 tenders involve removal of large amounts of constructionwaste consisting of road waste. No landfills for construction wasteexist in the Haifa area, and as a result, construction waste must behauled about 100 km to the nearest landfill. The landfill charges, per10 yard roll-off dumpster, amount to about $500. All 10 tenders are wonby different contractors, designated by letters A-J.

The Engineering Department of the city of Haifa employs an environmentalconsultant to ensure that construction waste from the construction worksin Haifa will not be illegally dumped in the Haifa vicinity. Theconsultant prepares detectable compositions in the form of white roadpaint comprising two different marker compounds, a compound comprisingLi and a compound comprising Br. The asphalt road surfaces to which thedetectable compositions are applied, as well as the non-markeringredients of the road paint, are analyzed, to determine that nodetectable amounts of Li or Br are present. Once the determination ismade, detectable compositions are prepared according to table 1 inlevels of parts per million, and are designated to specific constructionsites and contractors.

TABLE 1 Construction Site Contractor Li content (ppm) Br content (ppm) 1A 10 10 2 B 50 10 3 C 100 10 4 D 10 50 5 E 50 50 6 F 100 50 7 G 0 100 8H 10 100 9 I 50 100 10 J 100 100

The consultant prepares unique detectable compositions, according toTable 1, and applies this to road surfaces in areas which willpotentially be destroyed upon starting road construction by each of the10 contractors. The consultant applies detectable compositions at sites1-10 before construction begins, without the knowledge of contractors ofthe location and composition of the marking.

Upon finding illegally disposed construction waste, the Haifamunicipality may inform the consultant, who analyzes samples of theconstruction waste. The consultant finds, using X-Ray fluorescence, thata sample was marked with a detectable composition comprising 10 ppm ofLi and 100 ppm of Br. The consultant informs Haifa municipality that theillegally disposed waste is from construction site 8, under theresponsibility of contractor H. Haifa municipality may take legal actionagainst contractor H for illegally dumping waste materials.

As illustrated in the above example, the municipality was not aware ofthe correlation between specific markings and contractors to which themarkings corresponded. The consultant was the only entity aware of thecode corresponding specific markers to corresponding contractors. Thisprocess allows control and maintenance of codes outside of the hands ofmunicipalities. Furthermore, it allows for statewide or countrywidedatabases to monitor waste disposal.

Methods according to embodiments of the invention may use relativelyinexpensive marking compounds to provide hundreds of thousands ofpossibilities of unique markings of waste, associated with an equallylarge number of entities responsible for the disposal of the waste.

Descriptions of embodiments of the invention in the present applicationare provided by way of example and are not intended to limit the scopeof the invention. The described embodiments comprise different features,not all of which are required in all embodiments of the invention. Someembodiments utilize only some of the features or possible combinationsof the features. Variations of embodiments of the invention that aredescribed, and embodiments of the invention comprising differentcombinations of features noted in the described embodiments, will occurto persons of the art. The scope of the invention is limited only by theclaims.

The invention claimed is:
 1. An X-Ray Fluorescence (XRF) devicecomprising: a signal reading processor in communication with a radiationdetector, which is adapted for detecting X-Ray signals arriving from anobject in response to irradiation of the object by X-Ray or Gamma-Rayradiation, and providing data indicative of the detected X-Ray signals;said signal reading processor being adapted for receiving and processingthe detected X-Ray signals to identify signatures of materials includedin said object; wherein said processor comprises: a spectral dataprovider configured for determining data indicative of a wavelengthspectral profile of at least a portion of the detected X-Ray signals;and a filtration module adapted for filtering said data indicative ofthe wavelength spectral profile by applying time series analysis withrespect to a wavelength scale, to the wavelength spectral profile toidentify a non-stationarity profile with respect to said wavelengthscale, associated with a trend component of the wavelength spectralprofile; wherein said non-stationarity profile is associated with atleast one of noise and clutter in the X-Ray signal portion detected bysaid radiation detector; and said filtration module comprises astationarity filter adapted to apply said time series analysis to saidwavelength spectral profile to carry out at least stationarityfiltration for suppressing at least said non-stationarity profile toobtain a filtered profile having improved at least one of signal tonoise ratio and signal to clutter ratio, from which spectral peaksassociated with signatures of materials included in said object can beidentified with improved accuracy and reliability.
 2. The XRF deviceaccording to claim 1 wherein said filtration module comprises: aseasonality filter operative for applying the time series analysis withrespect to the wavelength scale, to suppress a seasonality profileindicative of a seasonal components with respect to a wavelength scaleand obtain a suppressed seasonality wavelength spectral profile; andwherein the stationarity filter is operative for processing saidsuppressed seasonality wavelength spectral profile to determine saidtrend component of the non-stationarity profile, which is to besuppressed to obtain said filtered profile.
 3. The XRF device accordingto claim 1 wherein said filtration module comprises: a seasonalityfilter operative for applying the time series analysis with respect tothe wavelength scale, to identify a seasonality profile indicative of aseasonal components with respect to a wavelength scale of the wavelengthspectral profile; and suppress the seasonal components from thewavelength spectral profile to obtain said filtered profile.
 4. The XRFdevice according to claim 1 wherein said processor is adapted forcarrying out the following: operating said filtration module to applysaid filtering to filter a plurality of wavelength spectral profiles ofa plurality of portions of the X-Ray signal arriving from the object ina plurality of time frames, to suppress trend components and periodiccomponents from said plurality of wavelength spectral profiles; andcomputing said filtered profile from data indicative of said pluralityof the wavelength spectral profiles being filtered.
 5. The XRF deviceaccording to claim 4 wherein computing said filtered profile comprisescalculating an average profile of said plurality of the wavelengthspectral profiles being filtered.
 6. The XRF device according to claim 1comprising an identification module configured and operable forprocessing said filtered profile to identify therein one or more peakssatisfying a predetermined condition and associated with XRF signaturesof materials included in said object; and a data storage storingassociation data associating information indicative of a plurality ofobjects with marking data indicative of a plurality of XRF markers usedfor marking the respective objects, whereby the marking data of eachrespective object is indicative of XRF signatures of one or morematerials of a respective XRF marker marking the object; and whereinsaid identification module identifies said object by associating themarking data of the XRF marker marking the object with the XRFsignatures of materials included in the object data obtained for saidobject.
 7. The XRF device according to claim 1 configured as a handheldXRF detection device; the XRF device comprises a communication moduleconfigured to communicate data indicative of said filtered profile to aremote processing center and to obtain from the processing center, inresponse, object data indicative of said object; and wherein one or moreof the following: i. the XRF device further comprises a position locatorconfigured to identify the position of the XRF device, and wherein saidcommunication module is capable of communicating data indicative of saidposition to said processing center together with said data of thefiltered profile; ii. the XRF device further comprises an optical readerconfigured to read an optical code associated with said object andwherein said communication module is capable of communicating dataindicative of said optical code to said processing center together withsaid data of the filtered profile; iii. the XRF device further comprisesa memory storing an identification code unique to the XRF device, andwherein the XRF device is configured to transmit the identification codeto a central computer via the communication module.
 8. The XRF deviceaccording to claim 1 wherein the radiation detector enables detection ofan XRF marker material marking said object and having concentration inthe order of 100s of ppb, and more preferably enables detection of XRFmarker material and having concentration in the order of 1 ppm.
 9. TheXRF device according to claim 1 comprising said radiation detector. 10.A method for authenticating an object marked with XRF marking, themethod comprising: filtering a wavelength spectral profile of a detectedportion of an X-Ray signal arriving from an object in response to X-Rayor Gamma-Ray radiation applied to the object; wherein said filteringcomprises applying time series analysis with respect to a wavelengthscale, to the wavelength spectral profile to identify a non-stationarityprofile with respect to said wavelength scale, associated with a trendcomponent of the wavelength spectral profile; wherein saidnon-stationarity profile is associated with at least one of noise andclutter in the X-Ray signal portion detected by said radiation detector;and wherein said filtering comprises suppressing at least saidnon-stationarity profile from the wavelength spectral profile to obtaina filtered profile having improved at least one of signal to noise ratioand signal to clutter ratio, from which spectral peaks associated withsignatures of materials included in said object can be identified withimproved accuracy and reliability; and identifying one or more peaks inthe filtered profile satisfying a predetermined condition therebyenabling utilizing wavelengths of said one or more peaks to identifysignatures of materials included in said object.
 11. The methodaccording to claim 10 wherein said filtering comprises: applying thetime series analysis with respect to the wavelength scale, to suppress aseasonality profile indicative of seasonal components with respect to awavelength scale and obtain a suppressed seasonality wavelength spectralprofile; and processing said suppressed seasonality wavelength spectralprofile to identify said non-stationarity profile.
 12. The methodaccording to claim 10 wherein said filtering further comprises: applyingthe time series analysis with respect to the wavelength scale, toidentify a seasonality profile indicative of a seasonal components withrespect to a wavelength scale of the wavelength spectral profile; andsuppressing the seasonal components from the wavelength spectral profileto obtain said filtered profile.
 13. The method according to claim 10comprising one or more of the following: irradiating said object withsaid radiation, detecting a portion of an X-Ray signal arriving from anobject in response to X-Ray or Gamma-Ray radiation applied to theobject; and applying spectral processing to the detected X-Ray signal toobtain data indicative of wavelength spectral profile thereof within acertain X-Ray band.
 14. The method according to claim 10 comprisingcarrying out said filtering for wavelength spectral profiles associatedwith a plurality of portions of the X-Ray signal arriving from theobject in a plurality of time frame portions of the X-Ray signaldetected during a plurality of time frames, and obtaining said filteredprofile by computing an average of a plurality of filtered spectralprofiles obtained by said filtering of the plurality of portions of theX-Ray signal obtained in said plurality of time frames respectively. 15.The method according to claim 10 wherein said one or more peakssatisfying the predetermined condition include peaks indicative of X-RayFluorescence (XRF) response of XRF materials marking said object; andwherein the method comprising utilizing said wavelengths and possiblymagnitudes of the one or more peaks to determine material dataindicative of types and concentrations of materials included in saidobject, and utilizing said material data to authenticate said object.16. The method according to claim 10 adapted for processing wavelengthspectral profile obtained by a handheld XRF detection device.
 17. Themethod according to claim 16 further comprising communicating dataindicative of said filtered profile to a remote processing center and toobtain from the processing center, in response, object data indicativeof said object.
 18. The method according to claim 17 comprisingutilizing an optical reader for reading an optical code associated withsaid object; and communicating data indicative of said optical code tosaid processing center together with said data of the filtered profile,in order to obtain said object data in response.
 19. The methodaccording to claim 17 comprising communicating data indicative of aunique identification code of the handheld XRF detection device to theremote processing center, in order to obtain said object data.
 20. Themethod according to claim 10 adapted for detection of an XRF markermarking said object and having concentration in the order of 100s ofppb, and more preferably enables detection of XRF marker havingconcentration in the order of 1 ppm.